TWI513723B - Process for continuous preparation of a prepolymer based on phenolic resins, oxazolines and epoxides - Google Patents
Process for continuous preparation of a prepolymer based on phenolic resins, oxazolines and epoxides Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
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- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
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Description
本發明描述一種使用觸媒連續製備建基於唑啉類、環氧化物及酚醛樹脂的預聚合物之方法,及其用途。The present invention describes a continuous preparation based on the use of a catalyst A method of prepolymerizing oxazolines, epoxides and phenolic resins, and uses thereof.
E.A. Boulter等人在Electrical Insulation Conference,1997,及Electrical Manufacturing & Coil Winding Conference Proceedings,第22至25卷(1997年9月),249至253頁中,描述經唑啉改質的酚醛樹脂之性質,像是,例如,對碳纖維、玻璃纖維及金屬的黏附力、對熱氧化性降解的耐性、火災事件時散發少量煙氣、低可燃性及高耐衝擊強度。由於該低可燃性,這些聚合物特別適用於製造航太產業的組件。其他應用為電絕緣領域及電子儀器領域。根據E.A. Boulter,這些前驅物及預聚合物也適用於包括射出成形、樹脂轉注成形(RTM)及預浸體的應用。EA Boulter et al., Electrical Insulation Conference, 1997, and Electrical Manufacturing & Coil Winding Conference Proceedings, Vol. 22-25 (September 1997), pages 249-253, describe The properties of azoline-modified phenolic resins, such as, for example, adhesion to carbon fibers, glass fibers and metals, resistance to thermal oxidative degradation, small amounts of fumes, low flammability and high impact strength during fire events . Due to this low flammability, these polymers are particularly suitable for the manufacture of components in the aerospace industry. Other applications are in the field of electrical insulation and electronic instrumentation. According to EA Boulter, these precursors and prepolymers are also suitable for applications including injection molding, resin transfer molding (RTM) and prepregs.
文獻中有描述雙官能基唑啉類與酚醛樹脂的反應。例如,專利說明書US 4,699,970描述酚醛樹脂與1,3-伸苯基雙唑啉在催化量的亞磷酸三苯酯存在下之反應。根據實施例,於225℃的溫度進行固化。所獲得的聚合物具有138至184℃的玻璃轉移溫度。Bifunctional groups are described in the literature. The reaction of oxazolines with phenolic resins. For example, the patent specification US 4,699,970 describes phenolic resins with 1,3-phenylene double The reaction of oxazoline in the presence of a catalytic amount of triphenyl phosphite. According to the examples, curing was carried out at a temperature of 225 °C. The polymer obtained had a glass transition temperature of 138 to 184 °C.
US 5,302,687也有描述1,3-伸苯基雙唑啉與酚醛樹脂在鏻鹽及/或銨鹽存在下的反應。此處同樣根據實施例於225℃進行固化,及聚合物同樣具有150至157℃的玻璃轉移溫度。US 5,302,687 also describes 1,3-phenylene double The reaction of an oxazoline with a phenolic resin in the presence of a phosphonium salt and/or an ammonium salt. The curing was also carried out here at 225 ° C according to the examples, and the polymer likewise had a glass transition temperature of 150 to 157 °C.
WO 2009/132924描述含酚醛樹脂的聚合物組成物,該聚合物組成物包含唑啉類及安定劑。所用的觸媒是亞磷酸三烷酯或亞磷酸三芳酯。該聚合物組成物較佳是藉由擠出機製備。WO 2009/132924 describes a polymer composition containing a phenolic resin, the polymer composition comprising Oxazolines and stabilizers. The catalyst used is a trialkyl phosphite or a triaryl phosphite. The polymer composition is preferably prepared by an extruder.
WO 2009/053581描述由環氧樹脂及可塑劑構成的樹脂組成物,該可塑劑具有溶解該環氧樹脂的功能且會影響黏度。WO 2009/053581 describes a resin composition composed of an epoxy resin and a plasticizer, which has a function of dissolving the epoxy resin and affects the viscosity.
該樹脂組成物可例如另外與交聯劑,如1,3-伸苯基雙唑啉類摻混。所用的觸媒例如包括路易士鹼類及路易士酸類,如三氟化硼-單乙基胺。該組成物可藉由簡單混合製備。固化溫度不高於195℃。The resin composition may, for example, additionally be combined with a crosslinking agent such as 1,3-phenylene The oxazoline is blended. The catalyst used includes, for example, Lewis bases and Lewis acids such as boron trifluoride-monoethylamine. The composition can be prepared by simple mixing. The curing temperature is not higher than 195 °C.
Hajime Kimura等人在Journal of Applied Polymer Science,第107卷,710至718頁(2008)描述由雙唑啉類及苯并類構成的樹脂組成物之製備方法,其使用磺酸及胺基醇或烷基胺的混合物作為觸媒(潛在的磺酸)。該樹脂係藉由批次方法製備。所獲得的聚合物具有介於149與186℃之間的玻璃轉移溫度。Hajime Kimura et al. in Journal of Applied Polymer Science, Vol. 107, pp. 710-718 (2008) described by Double Oxazolines and benzo A method of preparing a resin composition of the like, which uses a mixture of a sulfonic acid and an amino alcohol or an alkylamine as a catalyst (potential sulfonic acid). The resin was prepared by a batch process. The polymer obtained had a glass transition temperature between 149 and 186 °C.
本發明的目的在於提供一種建基於酚醛樹脂的預聚合物,其特徵為於酮類中的高溶解度及低於100℃的熔點。該預聚合物應該更特別適用於製造具有在140至200℃的範圍中之玻璃轉移溫度(Tg )之材料。It is an object of the present invention to provide a phenolic resin-based prepolymer characterized by high solubility in ketones and melting point below 100 °C. The prepolymer should be more particularly suitable for the manufacture of materials having a glass transition temperature ( Tg ) in the range of from 140 to 200 °C.
令人驚訝的是已經有人發現由唑啉組分、酚醛樹脂、環氧化物及觸媒製備預聚合物的連續方法。由於使用了觸媒,使該預聚合物可於較低固化溫度製備及/或與先前技藝方法相比可縮短固化時間。所得的聚合物之特徵為140至200℃的玻璃轉移溫度Tg 。Surprisingly, it has been discovered by A continuous process for the preparation of prepolymers from oxazoline components, phenolic resins, epoxides and catalysts. Due to the use of a catalyst, the prepolymer can be prepared at lower curing temperatures and/or can reduce cure time compared to prior art methods. The resulting polymer is characterized by a glass transition temperature T g of from 140 to 200 °C.
此外已顯示本發明的預聚合物可藉由擠出連續製備。相對於先前技藝載明的批次方法,擠出令人驚訝地帶來實質上沒有預先交聯的預聚合物之可能性。透過先確定成分的強烈混合及其次從時間和位置的觀點來看讓起始材料分開計量之擠出機的應用,可幾乎完全避免任何不想要的過早反應。從模具排出之後被冷凍皮帶快速冷卻的預聚合物使反應確定終止。因此,獲得非常低交聯度及其均質性顯著的預聚合物,及因此該預聚合物非常易溶於標準市售溶劑,例如像是酮類。本發明的方法也讓本發明的預聚合物具有一致的產物性質。It has furthermore been shown that the prepolymers of the invention can be prepared continuously by extrusion. Extrusion surprisingly brings the possibility of a prepolymer that is substantially free of pre-crosslinking, relative to the batch process set forth in the prior art. The application of an extruder that separately measures the starting material from the point of view of time and position from the point of view of the time and position can almost completely avoid any unwanted premature reaction. The prepolymer which is rapidly cooled by the freezing belt after being discharged from the mold terminates the reaction. Thus, a prepolymer having a very low degree of crosslinking and its homogeneity is obtained, and thus the prepolymer is very soluble in standard commercial solvents such as, for example, ketones. The process of the invention also allows the prepolymer of the invention to have consistent product properties.
關於呈樹脂轉注成形(RTM)系統的預聚合物之用途,例如用於溶液加工,用於玻璃纖維的塗覆,或用於製造預浸體,必須可取得不含凝膠的材料。先前技藝以批次製得的材料既不可溶於標準市售溶劑,亦沒有明載的熔點。相反地,本發明的預聚合物可溶於標準市售溶劑而實質上沒有殘餘物,並因此可輕易進一步加工。再者,本發明的預聚合物可付諸應用於包括電層疊體、運輸及航太產業領域的結構組件之製造。Regarding the use of prepolymers in resin transfer molding (RTM) systems, such as for solution processing, for glass fiber coating, or for the manufacture of prepregs, it is necessary to obtain a gel-free material. Materials previously prepared in batches are insoluble in standard commercial solvents and have no melting point. Conversely, the prepolymers of the present invention are soluble in standard commercial solvents without substantial residue and can therefore be readily processed further. Furthermore, the prepolymer of the present invention can be applied to the manufacture of structural components including the electrical laminate, transportation, and aerospace industries.
因此本發明提供一種在觸媒存在下連續製備建基於酚醛樹脂、唑啉組分及環氧化物的預聚合物之方法,該方法的特徵為以物流A將該酚醛樹脂和該唑啉組分供應至擠出機;及以物流B將作為觸媒之三氟化硼或三氯化鋁的路易士加成物、或芳磺酸類或烷磺酸類、或潛在的芳磺酸類或潛在的烷磺酸類供應至該擠出機;及以物流C將該環氧化物供應至該擠出機,當依擠出方向來看時該物流A的橫向進給係於該物流C的橫向進給之前,這些反應物係於120至200℃的反應溫度及3秒至15分鐘之於該擠出機中的滯留時間內混合;及接著於30至60秒內將該擠出機的排出產物冷卻至低於45℃的溫度。Therefore, the present invention provides a continuous preparation of a phenolic resin based on the presence of a catalyst. a method of pre-polymerizing an oxazoline component and an epoxide, the method characterized by the phenolic resin in stream A and The oxazoline component is supplied to the extruder; and the Lewis B adduct of boron trifluoride or aluminum trichloride as a catalyst, or the arylsulfonic acid or alkanesulfonic acid, or a latent aromatic sulfonic acid Or a potential alkane sulfonic acid is supplied to the extruder; and the epoxide is supplied to the extruder in stream C, the lateral feed of the stream A being attached to the stream C when viewed in the direction of extrusion Prior to the transverse feed, the reactants are mixed at a reaction temperature of 120 to 200 ° C and a residence time of 3 seconds to 15 minutes in the extruder; and then the extruder is placed within 30 to 60 seconds. The effluent product was cooled to a temperature below 45 °C.
本發明另提供一種由本發明的方法製得之預聚合物,及本發明的預聚合物之用途。The invention further provides a prepolymer prepared by the process of the invention and the use of the prepolymer of the invention.
為了達成本發明的目的,預聚合物係理解成主要是也可能含小比例聚合化合物的寡聚合化合物。相對於聚合物,該預聚合物還是可溶性及可塑性加工且根本上可藉由熱起始反應轉化成目標聚合物。術語“潛在的芳磺酸”或“潛在的烷磺酸”係理解成表示磺酸及胺基醇或烷基胺的混合物。For the purposes of the present invention, a prepolymer is understood to be an oligomeric compound which is predominantly also a small proportion of polymeric compound. The prepolymer is also soluble and malleable relative to the polymer and is fundamentally convertible to the target polymer by a thermal initiation reaction. The term "potential arylsulfonic acid" or "potential alkane sulfonic acid" is understood to mean a mixture of sulfonic acid and an amino alcohol or an alkylamine.
本發明的方法使用較佳是依據下列結構(1)的唑啉類作為唑啉組分The method of the present invention is preferably used in accordance with the following structure (1) Oxazoline Oxazoline component
其中R1 =C1-2 烷基或苯基,R2 、R3 及Rn =氫、C1-2 烷基,g=0、1、2、3,及/或依據結構(2)的雙唑啉類Wherein R 1 =C 1-2 alkyl or phenyl, R 2 , R 3 and R n = hydrogen, C 1-2 alkyl, g=0, 1, 2, 3, and/or according to structure (2) Double Oxazoline
其中A=亞甲基或伸苯基,R4 、R5 、R6 、R7 、Rm 、Ro =氫、C1-2 烷基,h、i=0、1、2、3,R1 、R2 、R3 、R4 、R5 、R6 、R7 、Rn 、Rm 及Ro 型的取代基可為相同或不同並經取代或未經取代,結構片斷A可經取代或未經取代,及m及o可為相同或不同。Wherein A = methylene or phenyl, R 4 , R 5 , R 6 , R 7 , R m , R o = hydrogen, C 1-2 alkyl, h, i = 0, 1, 2, 3, The substituents of the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R n , R m and R o type may be the same or different and substituted or unsubstituted, and the structural moiety A may be Substituted or unsubstituted, and m and o may be the same or different.
該結構片斷A可具有甲基及/或乙基作為取代基。R1 、R2 、R3 、R4 、R5 、R6 、R7 、Rn 、Rm 及Ro 型的取代基較佳為未經取代。The structural fragment A may have a methyl group and/or an ethyl group as a substituent. The substituents of the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R n , R m and R o type are preferably unsubstituted.
本發明的方法較佳使用具有R1 、R2 、R3 、R4 、R5 、R6 、R7 、Rn 、Rm 及Ro 型的取代基及未經取代的結構片斷A之依據結構(1)及/或(2)的化合物。較佳為使用依據結構(1)及/或(2)且g、h、i=0或1的化合物。The method of the present invention preferably uses a substituent having R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R n , R m and R o type and an unsubstituted structural moiety A. A compound according to structure (1) and/or (2). It is preferred to use a compound according to the structures (1) and/or (2) and g, h, i = 0 or 1.
本發明的方法之一較佳具體例使用依據結構(2)的雙唑啉類,其中m和o較佳為0或1。更特別的是使用結構片斷A具有伸苯基之依據結構(2)的雙唑啉類,如1,3-伸苯基雙唑啉或1,4-伸苯基雙唑啉。為了訂製該預聚合物的性質,也可使用唑啉類及雙唑啉類的混合物作為唑啉組分。A preferred embodiment of the method of the present invention uses a double according to the structure (2) Oxazolines, wherein m and o are preferably 0 or 1. More particularly, the use of structural segment A has a structure based on the structure of the phenyl group (2) Oxazoline, such as 1,3-phenylene Oxazoline or 1,4-phenylene double Oxazoline. In order to customize the properties of the prepolymer, it can also be used Oxazoline and double a mixture of oxazolines Oxazoline component.
在本發明的方法中,較佳是以起始材料的組成為基準,使用10重量%至90重量%,較佳30重量%至60重量%及更佳40重量%至55重量%的唑啉組分。In the method of the present invention, it is preferred to use 10% by weight to 90% by weight, preferably 30% by weight to 60% by weight and more preferably 40% by weight to 55% by weight based on the composition of the starting material. Oxazoline component.
在本發明的方法中,較佳是使用藉由縮合酚類與醛類,更特別的是甲醛,所獲得的酚醛樹脂。因此,在此方法中可使用選自酚醛清漆樹脂型及/或可溶酚醛樹脂型的酚醛樹脂。特佳是使用酚醛清漆樹脂作為酚醛樹脂(B)。在本發明的方法中,較佳是以起始材料的組成為基準,使用10重量%至90重量%,較佳30重量%至60重量%及更佳40重量%至50重量%的酚醛樹脂。In the method of the present invention, a phenol resin obtained by condensing a phenol with an aldehyde, more specifically formaldehyde, is preferably used. Therefore, a phenol resin selected from the group consisting of a novolac resin type and/or a resol type resin can be used in this method. It is particularly preferable to use a novolak resin as the phenol resin (B). In the method of the present invention, it is preferred to use 10% by weight to 90% by weight, preferably 30% by weight to 60% by weight and more preferably 40% by weight to 50% by weight, based on the composition of the starting material, of the phenolic resin. .
關於環氧化物,在本發明的方法中可使用依據結構(3)的單環氧化物With regard to the epoxide, a monoepoxide according to structure (3) can be used in the process of the invention.
其中R8 =氫、C1-3 烷基,結構(4)的二環氧化物Wherein R 8 = hydrogen, C 1-3 alkyl, the diepoxide of structure (4)
其中R9 及R10 =氫及C1-3 烷基,R9 及R10 可為相同或不同,或依據結構(5)及/或結構(6)的多官能基環氧化物Wherein R 9 and R 10 = hydrogen and C 1-3 alkyl, R 9 and R 10 may be the same or different, or a polyfunctional epoxide according to structure (5) and/or structure (6)
其中R11 =氫、C1-3 烷基或 Wherein R 11 = hydrogen, C 1-3 alkyl or
其中R12 =氫或C1-3 烷基。Wherein R 12 = hydrogen or C 1-3 alkyl.
在本發明的方法中較佳是使用由單環氧化物、二環氧化物及/或多環氧化物所組成的混合物作為環氧化物。該結構(3)及(6)較佳具有線性烷基。It is preferred in the process of the invention to use a mixture of monoepoxides, diepoxides and/or polyepoxides as the epoxide. The structures (3) and (6) preferably have a linear alkyl group.
在本發明的方法中較佳是以起始材料的組成為基準,使用1重量%至10重量%,較佳3重量%至8重量%及更佳4重量%至6重量%的環氧化物。Preferably, in the process of the present invention, from 1% by weight to 10% by weight, preferably from 3% by weight to 8% by weight and more preferably from 4% by weight to 6% by weight, based on the composition of the starting material, of the epoxide .
在本發明的方法之一特定具體實施例中也可另外供應結構(7)的苯并類The benzoic acid of structure (7) may also be additionally supplied in a specific embodiment of the method of the invention. class
其中A=(CR13 R14 )、SWhere A=(CR 13 R 14 ), S
R13 、R14 =H、C1-4 烷基R 13 , R 14 =H, C 1-4 alkyl
至擠出機。在180至190℃的區域中,這些化合物進行重排,從而提供其他酚的OH基團進行反應。To the extruder. In the region of 180 to 190 ° C, these compounds are rearranged to provide an OH group of other phenols for reaction.
在本發明的方法較佳是以起始材料的組成為基準,使用0重量%至10重量%,較佳是2重量%至9重量%及更佳是4重量%至8重量%的唑啉類。在本發明的方法之一特定具體實施例中沒使用苯并。Preferably, the process of the invention is based on the composition of the starting materials, from 0% to 10% by weight, preferably from 2% to 9% by weight and more preferably from 4% to 8% by weight. Oxazolines. No benzoic acid is used in a particular embodiment of the method of the invention .
關於本發明的方法中之觸媒,較佳是使用三氯化硼的路易士加成物,或潛在的芳磺酸類,更特別的是三氟化硼-乙基胺加成物、三氟化硼-甲醇加成物、三氟化硼-磷酸、對-甲苯磺酸/二乙醇胺或對-甲苯磺酸/1-胺基-2-丙醇。三氟化硼的路易士加成物於升高的溫度散發BF3 。由於氣態及其毒性,在本發明的方法中直接使用BF3 並不得當。關於替代物也可使用AlCl3 加成物。為了達成本發明的目的,潛在的芳磺酸類是磺酸類與供體化合物的加成物。更特別的是該供體化合物為胺基醇類或具有1至4個碳原子的烷基胺類。該潛在的芳磺酸特佳是磺酸與胺基醇或烷基胺,較佳胺基醇,的等莫耳混合物。不受理論束縛的是,假設潛在的芳磺酸類的案例將於升高的溫度釋出具有催化活性的磺酸類。With respect to the catalyst in the process of the present invention, it is preferred to use a Lewis Additive of boron trichloride or a latent arylsulfonic acid, more particularly a boron trifluoride-ethylamine adduct, trifluoroethylene. Boron-methanol adduct, boron trifluoride-phosphoric acid, p-toluenesulfonic acid/diethanolamine or p-toluenesulfonic acid/1-amino-2-propanol. The Lewis autoclave of boron trifluoride emits BF 3 at elevated temperatures. The direct use of BF 3 in the process of the invention is not appropriate due to the gaseous state and its toxicity. AlCl 3 adducts can also be used with regard to alternatives. For the purposes of the present invention, potential aryl sulfonic acids are adducts of sulfonic acids and donor compounds. More particularly, the donor compound is an amine alcohol or an alkylamine having from 1 to 4 carbon atoms. The latent aryl sulfonic acid is particularly preferably an equimolar mixture of a sulfonic acid and an amino alcohol or an alkylamine, preferably an amine alcohol. Without being bound by theory, it is assumed that the case of potential aryl sulfonic acids will release catalytically active sulfonic acids at elevated temperatures.
本發明的方法中之觸媒以起始材料的組成為基準,較佳使用0.2重量%至5重量%,較佳0.4重量%至4重量%及更佳0.5重量%至3重量%的量。The catalyst in the process of the present invention is preferably used in an amount of from 0.2% by weight to 5% by weight, preferably from 0.4% by weight to 4% by weight and more preferably from 0.5% by weight to 3% by weight, based on the composition of the starting materials.
有益的是把呈溶液態的路易士加成物觸媒供應至擠出機。在本發明的方法中,該觸媒較佳呈醇溶液,更佳呈乙醇溶液使用。醇中的觸媒量較佳是30重量%至50重量%。當使用芳磺酸類或烷磺酸類作為觸媒時,單獨或呈潛在的芳磺酸,有益的是呈熔融物而將其計量加入該擠出機。It is beneficial to supply the Lewis Lewis adduct catalyst in solution to the extruder. In the process of the present invention, the catalyst is preferably an alcohol solution, more preferably an ethanol solution. The amount of the catalyst in the alcohol is preferably from 30% by weight to 50% by weight. When arylsulfonic acids or alkanesulfonic acids are used as the catalyst, either alone or in the presence of a latent aryl sulfonic acid, it is beneficial to meter it into the extruder as a melt.
在本發明的方法中,該觸媒也是一樣,也可添加抗氧化劑,這較佳依起始材料進入該擠出機之一橫向進給完成。關於抗氧化劑較佳是使用所謂的立體受阻酚類,這些較佳是依據結構(8)的化合物,In the process of the invention, the catalyst is also the same, and an antioxidant may also be added, preferably in accordance with the lateral feed of the starting material into the extruder. As the antioxidant, it is preferred to use a so-called sterically hindered phenol, which is preferably a compound according to the structure (8).
其中Ra 、Rb 、Rc =氫、烷基、烷芳基或環烷基,Ra 、Rb 、Rc 型的取代基可為相同或不同及經取代或未經取代,像是,例如,依據結構(9)的4-甲基酚與二環戊二烯及異丁烯的反應產物,Wherein R a , R b , R c = hydrogen, alkyl, alkaryl or cycloalkyl, the substituents of the R a , R b , R c type may be the same or different and substituted or unsubstituted, as , for example, a reaction product of 4-methylphenol with dicyclopentadiene and isobutylene according to structure (9),
其中p=1至5。Where p = 1 to 5.
抗氧化劑在本發明的方法中較佳以起始材料的組成為基準,使用0.1重量%至2重量%,較佳0.2重量%至1.5重量%及更佳0.2重量%至1.2重量%的量。可使用的抗氧化劑之實例是LC或LC。The antioxidant is preferably used in the process of the invention in an amount of from 0.1% by weight to 2% by weight, preferably from 0.2% by weight to 1.5% by weight and more preferably from 0.2% by weight to 1.2% by weight, based on the composition of the starting materials. An example of an antioxidant that can be used is LC or LC.
在本發明的方法中,也可另外使用安定劑,較佳為使用所謂的HALS化合物(受阻胺光安定劑)-2,2,6,6-四甲基六氫吡啶-4-酮衍生物。也可添加不同HALS化合物的混合物。安定劑的添加能讓所得的聚合物之長期安定性獲得改善。In the method of the present invention, a stabilizer may also be additionally used, preferably a so-called HALS compound (hindered amine light stabilizer)-2,2,6,6-tetramethylhexahydropyridin-4-one derivative is used. . Mixtures of different HALS compounds can also be added. The addition of a stabilizer can improve the long-term stability of the resulting polymer.
在本發明的方法中較佳使用依據結構(10)的安定劑Preferably, the stabilizer according to structure (10) is used in the method of the present invention.
其中R’ =烷氧基、,及R” =氧自由基(-O‧)、氫、烷基或烷氧基、Wherein R ' = alkoxy, , and R ” = oxygen radical (-O‧), hydrogen, alkyl or alkoxy,
其中R’’’及RIV =烷基,RV =雜環及A’=伸烷基,及其中該烷基、烷氧基及伸烷基及雜環類係經取代或未經取代。Wherein R''' and R IV = alkyl, R V = heterocyclic ring and A'=alkylene group, and wherein the alkyl group, alkoxy group and alkylene group and heterocyclic ring are substituted or unsubstituted.
在本發明的方法中特佳是使用依據以下結構(11)至(13)的安定劑:It is particularly preferred in the process of the invention to use stabilizers according to the following structures (11) to (13):
其中RVII =氫、烷基或烷氧基,Wherein R VII = hydrogen, alkyl or alkoxy,
其中RVI =q=2至10,或Where R VI = q=2 to 10, or
其中RVIII =氫或烷基。Wherein R VIII = hydrogen or alkyl.
本發明的方法之另一個具體實施例使用所謂的被聚合物鍵結的HALS化合物,像是,例如,依據結構(14)的化合物Another embodiment of the method of the invention uses a so-called polymer-bound HALS compound, such as, for example, a compound according to structure (14)
其中RIX =氫或烷基及r、s10。Wherein R IX = hydrogen or alkyl and r, s 10.
這些被聚合物鍵結的HALS化合物是被鍵結於聚合物鏈上或中之2,2,6,6-四甲基六氫吡啶-4-酮衍生物。These polymer-bonded HALS compounds are 2,2,6,6-tetramethylhexahydropyridin-4-one derivatives bonded to or in the polymer chain.
特別是,安定劑在本發明的方法中係以起始材料的組成為基準,使用0.1重量%至2重量%,較佳0.2重量%至1.5重量%及更佳0.3重量%至1.2重量%的量。In particular, the stabilizer is used in the process of the invention on the basis of the composition of the starting materials, using from 0.1% by weight to 2% by weight, preferably from 0.2% by weight to 1.5% by weight and more preferably from 0.3% by weight to 1.2% by weight. the amount.
在本發明的方法中,較佳是不僅把立體受阻酚類,還有HALS化合物摻混於起始材料。In the process of the present invention, it is preferred to incorporate not only the sterically hindered phenols but also the HALS compound into the starting materials.
在本發明的方法之另一個具體實施例中,該安定劑及/或抗氧化劑可於其後在下游組合件中摻混於預聚合物。In another embodiment of the method of the present invention, the stabilizer and/or antioxidant can be subsequently blended into the prepolymer in a downstream assembly.
在本發明的方法中有益的是把添加物像是,例如,脫揮發物劑(devolatilizer)、脫泡劑或所謂的流動控制添加物加於起始材料。關於添加物可使用由,例如BYK以商品名稱-A 506、-A 525、-A 530、BYK-054、-R 605、-R 606或-A 535販售之類的,例如矽油或經矽酮改質的聚二醇類及聚醚類、消泡聚矽氧烷或聚合物、經聚醚改質的聚甲基烷基矽氧烷類。這些添加物的添加具有使預聚合物中及其後材料中的氣泡之形成能顯著減少之優點。添加物或二或多種這些添加物的混合物較佳是以起始材料的組成為基準,依0.1重量%至1重量%,較佳0.2重量%至0.8重量%及極佳0.3重量%至0.7重量%的量添加。It is advantageous in the process of the invention to add an additive such as, for example, a devolatilizer, a defoaming agent or a so-called flow control additive to the starting material. About the additive can be used by, for example, BYK under the trade name -A 506, -A 525, -A 530, BYK-054, -R 605, -R 606 or -A 535 sold, such as eucalyptus or fluorenone modified polyglycols and polyethers, defoaming polyoxyalkylenes or polymers, polyether modified polymethylalkyl oxime Alkanes. The addition of these additives has the advantage of significantly reducing the formation of bubbles in the prepolymer and subsequent materials. The additive or a mixture of two or more of these additives is preferably based on the composition of the starting material, from 0.1% by weight to 1% by weight, preferably from 0.2% by weight to 0.8% by weight, and preferably from 0.3% by weight to 0.7% by weight. The amount of % is added.
此外,可把鹵化及未經鹵化的難燃劑加於該預聚合物,在本發明的方法中較佳是以起始材料的組成為基準,使用1重量%至10重量%的難燃劑。Further, a halogenated and non-halogenated flame retardant may be added to the prepolymer, and in the method of the present invention, it is preferred to use 1% by weight to 10% by weight of the flame retardant based on the composition of the starting material. .
當使用本發明的預聚合物溶液時,建議添加流動控制劑、潤濕劑、脫揮發物劑、其他溶劑及無機添加物,像是沉澱氧化矽,以帶來判別準則的改良,包括表面黏附、整平情況及耐火性。因此,在本發明的方法中,較佳是以起始材料的組成為基準,使用0.5重量%至5重量%,更佳是2重量%至4重量%,的沉澱氧化矽,該氧化矽是,例如,以商品名稱50販售的種類。When using the prepolymer solution of the present invention, it is recommended to add a flow control agent, a wetting agent, a devolatilizer, other solvents, and inorganic additives, such as precipitated cerium oxide, to improve the discrimination criteria, including surface adhesion. , leveling and fire resistance. Therefore, in the method of the present invention, it is preferred to use 0.5% by weight to 5% by weight, more preferably 2% by weight to 4% by weight, based on the composition of the starting material, of precipitated cerium oxide, which is , for example, by product name 50 types of sale.
其他添加物來自耐衝擊改質劑的領域;因此本發明的方法中可以起始材料的組成為基準,使用,例如1重量%至15重量%的耐衝擊改質劑。Other additives come from the field of impact modifiers; therefore, in the process of the invention, the composition of the starting materials can be used as a basis, for example, from 1% by weight to 15% by weight of the impact modifier.
此外,有益的是在本發明的方法中使用至少一種脫模劑。這讓成形方法中的聚合物組成管理獲得改善。在本發明的方法中較佳是使用選自以下的脫模劑Furthermore, it is beneficial to use at least one release agent in the process of the invention. This allows an improvement in the management of the polymer composition in the forming process. In the method of the present invention, it is preferred to use a release agent selected from the group consisting of
- 聚矽氧烷,呈例如油、於水中的油乳化液、脂肪及樹脂的形式,- polyoxane, in the form of, for example, oil, oil emulsion in water, fat and resin,
- 蠟,實例是有及沒有官能基的天然及合成烷烴類,- waxes, examples of natural and synthetic alkanes with and without functional groups,
- 脂肪酸的金屬皂類或金屬鹽類,像是硬脂酸鈣、鉛、鎂、鋁及/或鋅,- metal soaps or metal salts of fatty acids such as calcium stearate, lead, magnesium, aluminum and/or zinc,
- 油脂,- grease,
- 聚合物,實例是聚乙烯醇類、聚酯類及聚烯烴類,- Polymers, examples being polyvinyl alcohols, polyesters and polyolefins,
- 磷酸單酯類,- Phosphate monoesters,
- 氟化烴類及/或- Fluorinated hydrocarbons and / or
- 無機脫模劑,像是石墨粉、滑石粉及雲母粉。- Inorganic release agents such as graphite powder, talc and mica powder.
關於脫模劑藉由本發明的方法製備之預聚合物較佳包含內脫模劑系統,該內脫模劑系統係加於本發明方法的起始材料中及在成形作業時主要累積於模製品表面上或能造成該表面更快速的固化,藉以預防模壁與模製品之間的任何結合。在本發明的方法中更特別的是使用Acmos Chemie KG公司的脫模劑,其係以商品名稱82-837、82-847、82-860、82-866、82-9018及82-853販售。在本發明的方法中該脫模劑更佳是以起始材料的組成為基準,以0.1重量%至2重量%的量,非常佳的是0.2重量%至1.5重量%使用。The prepolymer prepared by the process of the present invention preferably comprises an internal release agent system which is added to the starting material of the process of the invention and which is mainly accumulated in the molding during the forming operation. The surface may or may cause a faster cure of the surface to prevent any bond between the mold wall and the molded article. More particularly in the process of the invention is the use of a release agent from Acmos Chemie KG, which is sold under the trade name 82-837, 82-847, 82-860, 82-866, 82-9018 and 82-853 is for sale. In the process of the invention, the release agent is more preferably used in an amount of from 0.1% by weight to 2% by weight, very preferably from 0.2% by weight to 1.5% by weight, based on the composition of the starting material.
再者,在此方法中也可使用以起始材料的組成為基準,較佳為0.1重量%至2重量%的量之潤濕劑,較佳是表面活性劑,更佳是乙氧基化脂肪醇類或硫酸月桂酯鈉鹽。Further, a wetting agent, preferably a surfactant, more preferably an ethoxylated group, based on the composition of the starting material, preferably in an amount of from 0.1% by weight to 2% by weight, may be used in the process. Fatty alcohols or sodium lauryl sulfate.
本發明的方法中之起始材料的強烈混合係配合供熱於擠出機中完成。配合供熱的強烈混合及短暫反應意指起始材料於該擠出機中之滯留時間通常為3秒至15分鐘,較佳是3秒至5分鐘,更佳是5至180秒及非常佳是30至90秒。在此時期中該起始材料配合供熱短暫但強烈混合並可能部分引起反應。依據起始材料及最終產物的本質,這些滯留時間及溫度的圖形可能會變化。The intensive mixing of the starting materials in the process of the invention is accomplished by heating in an extruder. The intensive mixing and transient reaction with the heating means that the residence time of the starting material in the extruder is usually from 3 seconds to 15 minutes, preferably from 3 seconds to 5 minutes, more preferably from 5 to 180 seconds, and very good. It is 30 to 90 seconds. During this period the starting material cooperates with heat for a brief but intense mixing and may partially cause a reaction. These retention time and temperature patterns may vary depending on the nature of the starting materials and the final product.
因為本發明方法的目標在於製備一種預聚合物,所以較佳是利用選定溫度、滯留時間及物流的供應達成以所用的唑啉為基準僅不多於5%的轉化率。在本發明方法之一特佳具體實施例中,沒有轉化率。Since the object of the process of the invention is to prepare a prepolymer, it is preferred to use the selected temperature, residence time and supply of the stream to achieve The oxazoline is based on a conversion of no more than 5%. In a particularly preferred embodiment of one of the methods of the invention, there is no conversion.
設備如單螺桿或多螺桿擠出機,更特別是雙螺桿擠出機、行星轉子擠出機(planetary roller extruder)或環狀擠出機特別適用於本發明方法的擠出機且為偏好使用者。在本發明方法之一特定具體實施例中可使用多軸擠出機,如環狀擠出機。特佳是使用多螺桿擠出機,更特別是雙螺桿擠出機,及多軸擠出機,更特別是環狀擠出機。尤其佳是雙螺桿擠出機。Equipment such as single or multi-screw extruders, more particularly twin-screw extruders, planetary roller extruders or ring-shaped extruders, are particularly suitable for use in the extruder of the process of the invention and are preferred By. A multi-axis extruder, such as a ring extruder, can be used in a particular embodiment of the process of the invention. It is particularly preferred to use a multi-screw extruder, more particularly a twin-screw extruder, and a multi-axis extruder, more particularly a ring extruder. Especially preferred is a twin screw extruder.
較佳以分開物流將起始材料計量加入該擠出機,以免該預聚合物過早固化。因此,較佳是使用多筒式擠出機。用於本發明之目的的多筒式擠出機意指圍繞螺桿的套筒分成不同區,該不同區可分開加熱或冷卻。在被稱為筒的這些不同區中,也可分開地從另一者供應物流。依此方式,物流可被明確地供於該擠出機的不同位置,及個別物流的組成可以不同。Preferably, the starting material is metered into the extruder in a separate stream to prevent premature curing of the prepolymer. Therefore, it is preferred to use a multi-cylinder extruder. A multi-cylinder extruder for the purpose of the present invention means that the sleeve surrounding the screw is divided into different zones which can be separately heated or cooled. In these different zones, referred to as cartridges, the streams may also be supplied separately from the other. In this way, the streams can be explicitly supplied to different locations of the extruder, and the composition of the individual streams can vary.
第1圖概略描述此多筒式擠出機之一示範構造;Figure 1 schematically depicts an exemplary construction of this multi-cylinder extruder;
(a) 物流A之計量供料(a) Measurement supply of logistics A
(b) 物流B之計量供料(b) Measurement supply of logistics B
(c) 產物排放位置(出口溫度的測量位置)(c) Product discharge position (measurement position of outlet temperature)
(d) 冷卻皮帶(d) Cooling belt
(e) 造粒機(e) Granulator
(f) 細粒(f) Fine particles
(g) 分成8個不同區(習稱為筒)的套筒(g) a sleeve divided into 8 different zones (known as cartridges)
(h) 螺桿傳動(h) Screw drive
(i) 該擠出機的頭部(頭部溫度的測量位置)(i) the head of the extruder (measurement position of the head temperature)
(k) 物流C的計量供料(k) Measurement supply of logistics C
本發明方法的擠出機之不同筒較佳具有不同溫度。正好毗鄰該螺桿傳動的筒較佳具有低於反應溫度的溫度(溫度區TZ1),更佳是30至100℃。該產物排出位置的筒具有低於反應溫度的溫度(溫度區TZ3),更佳是100至160℃。設於該擠出機中央的筒具有所欲的反應溫度(溫度區TZ2),其在本發明方法的案例中是160至200℃,較佳是170至190℃及更佳是175至185℃。The different barrels of the extruder of the process of the invention preferably have different temperatures. The cylinder just adjacent to the screw drive preferably has a temperature lower than the reaction temperature (temperature zone TZ1), more preferably 30 to 100 °C. The cylinder at the discharge position of the product has a temperature lower than the reaction temperature (temperature zone TZ3), more preferably 100 to 160 °C. The cartridge disposed in the center of the extruder has a desired reaction temperature (temperature zone TZ2) which is 160 to 200 ° C, preferably 170 to 190 ° C and more preferably 175 to 185 ° C in the case of the method of the present invention. .
在本發明的上下文中,術語“反應溫度”意義與以顯著轉化率為特徵的反應不同;而是,在本發明的方法中,目標是5%的最大轉化率,但是較佳是沒轉化。In the context of the present invention, the term "reaction temperature" means a difference from a reaction characterized by a significant conversion; rather, in the process of the invention, the target is a maximum conversion of 5%, but preferably no conversion.
在本發明的方法中較佳是於一個物流A中供應酚醛樹脂及唑啉組分至該擠出機,該計量供料較佳是於帶有溫度區TZ1的擠出機筒中發生及更佳是於正好毗鄰該螺桿傳動的第一個筒中發生。In the process of the present invention, it is preferred to supply the phenolic resin in a stream A and The oxazoline component is fed to the extruder, preferably in the extruder barrel with temperature zone TZ1 and more preferably in the first cylinder just adjacent to the screw drive.
非常有益的是於單獨物流B或物流C中供應環氧化物及觸媒至該擠出機,該物流B及C較佳是被供入溫度區TZ2的位於中央之筒或被供入溫度區TZ3的產物排出位置之前的筒。該供料較佳發生於最靠近產物排出位置的溫度區TZ2之筒中。該二物流B及C更佳是被分開供應至該擠出機,當該觸媒呈溶液態供應至該擠出機時這尤其有益。It is highly advantageous to supply the epoxide and catalyst to the extruder in separate streams B or C, which are preferably fed to the central zone of the temperature zone TZ2 or to the temperature zone. The product of the TZ3 is discharged from the barrel before the position. The feed preferably occurs in the barrel of the temperature zone TZ2 closest to the product discharge location. Preferably, the two streams B and C are supplied separately to the extruder, which is especially beneficial when the catalyst is supplied to the extruder in solution.
在本發明方法之一特定具體實施例中,物流B,附帶條件為該觸媒係呈固態而非溶液,可被供應至該擠出機前面的物流A,所以物流A及B共同被供應至該擠出機。該二物流A及B共同計量供料較佳發生於溫度區TZ1,及特佳是該共同計量供料發生於正好毗鄰該螺桿傳動的第一個筒中。In a particular embodiment of the process of the invention, stream B, with the proviso that the catalyst is in a solid state rather than a solution, can be supplied to stream A in front of the extruder, so streams A and B are supplied together to The extruder. The two metered A and B co-metered feeds preferably occur in the temperature zone TZ1, and particularly preferably the co-metered feed occurs in the first cylinder adjacent the screw drive.
把可行的添加物,像是脫泡劑、脫揮發物劑、安定劑或抗氧化劑,例如,供應至該擠出機的較佳是物流A。然而,也可於另一個獨立於該二物流A及B以外的供料口把添加物供應至該擠出機之一筒。A viable additive such as a defoaming agent, a devolatilizer, a stabilizer or an antioxidant, for example, supplied to the extruder is preferably stream A. However, it is also possible to supply the additive to one of the extruders at a supply port other than the two streams A and B.
隨後的冷卻較佳迅速進行並且可併入該擠出機中。然而,此外,可在該擠出機下游使用管束、旋管、冷卻輥、空氣運送機及金屬輸送帶。Subsequent cooling is preferably carried out quickly and can be incorporated into the extruder. In addition, however, tube bundles, coils, chill rolls, air conveyors, and metal conveyor belts can be used downstream of the extruder.
轉化依據離開該擠出機的預聚合物之黏度初步藉由相應的前述設備進一步冷卻至適當溫度。接著藉由軋碎機、針盤磨機、錘擊研磨機或製片輥軋機等造粒或粉碎至所欲粒徑。The conversion is initially further cooled to the appropriate temperature by the corresponding apparatus described above, depending on the viscosity of the prepolymer leaving the extruder. Then, it is granulated or pulverized to a desired particle diameter by a crusher, a pin mill, a hammer mill or a tablet rolling mill.
藉由本發明的方法獲得之預聚合物的特徵是可溶於酮類,更佳是溶於2-丁酮,中形成澄清溶液,附帶條件是沒有使用固體,其係例如本發明的方法中之添加物沉澱氧化矽。再者,本發明的預聚合物較佳具有60至120℃的熔融範圍,較佳是77至116℃。The prepolymer obtained by the process of the invention is characterized by being soluble in ketones, more preferably in 2-butanone, forming a clear solution, with the proviso that no solids are used, such as in the process of the invention The additive precipitates cerium oxide. Further, the prepolymer of the present invention preferably has a melting range of 60 to 120 ° C, preferably 77 to 116 ° C.
本發明的預聚合物的這些性質使其與不溶於2-丁酮之先前技藝的預聚合物有所區隔。再者,先前技藝的產物無法測定熔點,因為其一般會事先分解。These properties of the prepolymer of the present invention distinguish it from the prior art prepolymer which is insoluble in 2-butanone. Furthermore, the products of the prior art cannot measure the melting point because it generally decomposes in advance.
本發明的預聚合物之性質也點出相對於先前技藝方法的產物之更低許多的交聯度。本發明的預聚合物因此可依於酮(例如,像是2-丁酮)中的溶液形式塗敷於支撐材料,如玻璃纖維或碳纖維。該預聚合物藉由粉末技術塗敷也可行,因為本發明的預聚合物具有一個熔點及因此能被熔融而不會分解。The nature of the prepolymer of the present invention also points to a much lower degree of crosslinking than the products of prior art methods. The prepolymer of the present invention can thus be applied to a support material such as glass fiber or carbon fiber in the form of a solution in a ketone (e.g., such as 2-butanone). The prepolymer is also feasible by powder technology because the prepolymer of the present invention has a melting point and thus can be melted without decomposition.
本發明另外提供的是本發明的預聚合物用於製造材料,更特別的是複合材料,更佳是纖維複合材料的用途。除了其用於製造複合材料的用途以外,本發明的預聚合物也可用於製造塑膠。這些製造出來的塑膠較佳具有140至200℃及更佳是175至190℃的玻璃轉移溫度,Tg ,及這些材料較佳是不含甲醛。Further provided by the invention is the use of the prepolymer of the invention for the manufacture of materials, more particularly composite materials, more preferably fiber composite materials. In addition to its use for the manufacture of composite materials, the prepolymers of the invention can also be used to make plastics. These manufactured plastics preferably have a glass transition temperature of 140 to 200 ° C and more preferably 175 to 190 ° C, T g , and these materials are preferably free of formaldehyde.
依據用途的類型,本發明的預聚合物可先溶於標準市售溶劑中,更特別的是酮類,較佳是2-丁酮。Depending on the type of use, the prepolymer of the present invention may be first dissolved in a standard commercial solvent, more particularly a ketone, preferably 2-butanone.
在上述預聚合物的發明性用途中可使用無機強化纖維(例如玻璃纖維)、有機強化纖維(例如醯胺纖維)、或碳纖維、金屬強化纖維或天然纖維。這些案例中的強化纖維可呈編織物、無緯稀洋紗、多軸稀洋紗、不纖布、針織物、織帶或蓆的形式使用。Inorganic reinforcing fibers (for example, glass fibers), organic reinforcing fibers (for example, guanamine fibers), or carbon fibers, metal reinforcing fibers or natural fibers can be used in the inventive use of the above prepolymer. The reinforcing fibers in these cases can be used in the form of woven fabrics, weftless scrims, multiaxial scrims, non-fibrous fabrics, knitted fabrics, webbing or mats.
本發明的預聚合物較佳是先溶於酮,更佳溶於2-丁酮,及接著以本發明的預聚合物之溶液浸潤強化纖維,較佳是玻璃纖維或碳纖維,及最後進行固化。The prepolymer of the present invention is preferably first dissolved in a ketone, more preferably in 2-butanone, and then impregnated with a solution of the prepolymer of the present invention, preferably a glass fiber or carbon fiber, and finally cured. .
在此發明案的上下文中,上述預聚合物係用作為基質。因而此預聚合物可用於,例如,製造預浸中間產物,如片狀成形材料(SMC)或塊狀成形材料(BMC)。預成形也可用於製造此發明性用途中的中間產物。In the context of this invention, the above prepolymer is used as a matrix. Thus the prepolymer can be used, for example, to make prepreg intermediates such as sheet forming materials (SMC) or bulk forming materials (BMC). Preforming can also be used to make intermediates in this inventive use.
此預聚合物配合強化材料加工形成複合材料可藉由依據先前技藝的多種方法/技術完成。更特別的是該複合材料係藉由以下列出的技術之一製造:The processing of the prepolymer with the reinforcing material to form the composite can be accomplished by a variety of methods/techniques in accordance with prior art techniques. More particularly, the composite is manufactured by one of the techniques listed below:
- 層疊,包括手工層疊,- cascading, including manual cascading,
- 預浸漬技術,- pre-impregnation technology,
- 樹脂轉注成形(RTM),- Resin transfer forming (RTM),
- 灌注方法,如樹脂灌注成形(RIM)或西門(Seeman)複合材料樹脂灌注法(SCRIMP),- Infusion methods such as resin infusion forming (RIM) or Seeman composite resin infusion (SCRIMP),
- 繞線法,- Winding method,
- 拉擠成形法或- Pultrusion or
- 纖維平伏法(fibre laying processes)。- fibre laying processes.
在該發明性用途中此預聚合物可藉由溫度的供應,於例如烘箱中、於壓力鍋中或於壓燙機中,或使用微波固化。In this inventive use the prepolymer can be cured by means of a temperature, for example in an oven, in a pressure cooker or in a press, or using microwaves.
藉由此發明性用途製造的複合材料可用於尤其是空中旅遊業、運輸(如汽車業)及電氣工業的領域。這些複合材料用於風力發電廠、輸送管或呈儲槽或壓力槽形式的容器。Composite materials made by this inventive use are useful in the fields of, inter alia, aerial tourism, transportation (such as the automotive industry) and the electrical industry. These composite materials are used in wind power plants, ducts or in the form of tanks or pressure tanks.
該預聚合物也可用於製造輕質構造,尤其是結合多層構造,如建基於酚醛樹脂、聚醯亞胺、玻璃、聚胺酯、聚醯胺或聚氯乙烯的蜂巢或發泡物。The prepolymers can also be used in the manufacture of lightweight constructions, especially in combination with multilayer constructions such as honeycombs or foams based on phenolic resins, polyimine, glass, polyurethane, polyamide or polyvinyl chloride.
把該預聚合物用於材料中造成特別是具有高耐熱變形性、高玻璃轉移溫度Tg 的組分。此預聚合物的高韌性及恢復力也有益於造成改良的耐衝擊性。The material for the prepolymer caused particularly having high heat distortion resistance, high glass transition temperature, T g component. The high toughness and restoring power of this prepolymer is also beneficial for resulting in improved impact resistance.
該預聚合物或源於該預聚合物的材料之其他應用領域是,例如,研磨料、耐火產物、鑄造工業、電池隔板、壓縮及射出成形、礦物綿(尤其是由玻璃、岩石或玄武岩(不含甲醛)組成者)、紙張含浸潤、用於電氣絕緣之建基於玻璃或紙張的層疊體、用於製造發泡物、玻璃或金屬之塗層(例如作為電纜保護)、於橡膠混合物中作為酚醛清漆的替代物、作為獨立相及與其他熱固物(如雙馬來亞醯胺)的共反應物。Other fields of application of the prepolymer or materials derived from the prepolymer are, for example, abrasives, refractory products, foundry industry, battery separators, compression and injection molding, mineral wool (especially from glass, rock or basalt) (formaldehyde-free) component, paper impregnated, glass or paper-based laminate for electrical insulation, foam or glass or metal coating (for example as cable protection), rubber mixture Used as a substitute for novolacs, as a separate phase and as a co-reactant with other thermosets such as bismaleimide.
本發明的預聚合物較佳可用於製造預浸體。為了達成本發明的目的,預浸體(預浸纖維的縮寫形式)表示由連續纖維及由本發明的預聚合物組成之未固化基質所構成的中間產物。可用於此產物的連續纖維包括玻璃纖維、碳纖維及醯胺纖維。本發明的預聚合物較佳是呈粉末而用於製造這些預浸體。The prepolymer of the present invention is preferably useful for making prepregs. For the purpose of the present invention, the prepreg (abbreviated form of prepreg) represents an intermediate product composed of continuous fibers and an uncured matrix composed of the prepolymer of the present invention. Continuous fibers useful in this product include glass fibers, carbon fibers, and guanamine fibers. The prepolymer of the present invention is preferably used in the manufacture of these prepregs in powder form.
以下的實施例意圖更詳細地解釋本發明的方法,而非意圖把本發明侷限於此具體實施例。The following examples are intended to explain the method of the invention in more detail, and are not intended to limit the invention to this particular embodiment.
在布拉本德(Brabender)W 30捏合艙中於160℃及50 rpm混合14.30g的1,3-伸苯基雙唑啉、13.91g的酚醛樹脂(來自Sumitomo-Bakelite的33100)、1.50g的環氧化物(來自Aldrich的506環氧樹脂)及0.30g的觸媒。為了防止產物被擠出筒,該捏合設備的衝頭(ram)以槓桿稱重為1 kg重。經過正好數分鐘之後,不再捏合混合物,就這樣停止混合作業。表1中彙總所用的觸媒及結果。Mix 14.30g of 1,3-phenylene double in a Brabender W 30 kneading chamber at 160 ° C and 50 rpm Oxazoline, 13.91 g of phenolic resin (from Sumitomo-Bakelite 33100), 1.50 g of epoxide (from Aldrich 506 epoxy resin) and 0.30 g of catalyst. In order to prevent the product from being squeezed out of the barrel, the ram of the kneading apparatus was weighed by a lever to a weight of 1 kg. After just a few minutes, the mixture is no longer kneaded and the mixing operation is stopped. The catalysts and results used are summarized in Table 1.
傳統於捏合艙中混合組分造成固化產物的熔點或分解溫度高於300℃及因此將其認定為不合於作為預聚合物。Conventionally, the mixed components in the kneading chamber cause the melting point or decomposition temperature of the cured product to be higher than 300 ° C and thus it is considered to be incompatible with the prepolymer.
使14.30g的1,3-伸苯基雙唑啉及13.90g的酚醛樹脂(來自Sumitomo-Bakelite的33100)在玻璃燒杯中於160℃的浴溫熔融約30分鐘;隨後,配合攪拌,加入1.50g的環氧化物(來自Aldrich的506環氧樹脂)及0.30g的觸媒。在該觸媒添加之後數分鐘,不再攪拌混合物。表2中彙總所用的觸媒及結果。Making 14.30g of 1,3-phenylene double Oxazoline and 13.90 g of phenolic resin (from Sumitomo-Bakelite 33100) Melt in a glass beaker at a bath temperature of 160 ° C for about 30 minutes; then, with stirring, add 1.50 g of epoxide (from Aldrich) 506 epoxy resin) and 0.30 g of catalyst. A few minutes after the addition of the catalyst, the mixture was no longer stirred. The catalysts and results used are summarized in Table 2.
即使後來再將該環氧化物及觸媒加至該混合物仍造成固化產物的熔點或分解溫度高於300℃及因此將其認定為不合於作為預聚合物。Even if the epoxide and catalyst are later added to the mixture, the melting point or decomposition temperature of the cured product is higher than 300 ° C and thus it is considered to be incompatible with the prepolymer.
使14.30g的1,3-伸苯基雙唑啉及13.90g的酚醛樹脂(來自Sumitomo-Bakelite的33100)在玻璃燒杯中於160℃的浴溫熔融約30分鐘;隨後,配合攪拌,加入1.50g的環氧化物(來自Aldrich的506環氧樹脂)及0.30g的亞磷酸三苯酯作為觸媒。讓起始材料再攪拌5分鐘及接著使該熔融物冷卻至室溫。該預聚合物的熔融範圍是85.5至101℃及玻璃轉移溫度Tg 是137℃,且固化係於180℃的溫度進行6小時。Making 14.30g of 1,3-phenylene double Oxazoline and 13.90 g of phenolic resin (from Sumitomo-Bakelite 33100) Melt in a glass beaker at a bath temperature of 160 ° C for about 30 minutes; then, with stirring, add 1.50 g of epoxide (from Aldrich) 506 epoxy resin) and 0.30 g of triphenyl phosphite as a catalyst. The starting material was stirred for a further 5 minutes and then the melt was allowed to cool to room temperature. The prepolymer had a melting range of 85.5 to 101 ° C and a glass transition temperature T g of 137 ° C, and the curing was carried out at a temperature of 180 ° C for 6 hours.
使用亞磷酸三苯酯作為觸媒所得的預聚合物能得出玻璃轉移溫度Tg 僅137℃之材料。A prepolymer obtained using triphenyl phosphite as a catalyst can give a material having a glass transition temperature T g of only 137 °C.
實施例7至10係於來自布拉本德(Brabender)的DSE 25雙螺桿擠出機中進行,該擠出機由8個分開的加熱及冷卻的筒組成(參見第1圖)。Examples 7 to 10 were carried out in a DSE 25 twin-screw extruder from Brabender consisting of 8 separate heated and cooled cylinders (see Figure 1).
擠出機的筒溫依下列設定:The barrel temperature of the extruder is set as follows:
‧ 筒0:35至45℃‧ Cartridge 0: 35 to 45 ° C
‧ 筒1:86至100℃‧ Cartridge 1: 86 to 100 ° C
‧ 筒2至5:180℃‧ Cartridge 2 to 5: 180 ° C
‧ 筒6:120至160℃‧ Cartridge 6: 120 to 160 ° C
‧ 筒7:100至110℃‧ Cartridge 7: 100 to 110 ° C
‧ 頭部溫度:100至160℃‧ Head temperature: 100 to 160 ° C
‧ 出口溫度:148至154℃‧ Exit temperature: 148 to 154 ° C
所有固態組分(使用的酚醛樹脂、唑啉、安定劑、抗氧化劑、難燃劑)-除了環氧化物及觸媒以外-以機械方式預混合並經由計量料斗(參見第1圖的(a))輸入至該擠出機的筒0。同時計量的是輸入至筒5之來自兩個不同儲存容器的環氧化物(具有100℃的夾套溫度之儲存容器,參見第1圖的(k))及觸媒溶液(參見第1圖的(b))。該觸媒係呈具有20重量%至44重量%濃度(strength)的溶液輸入至該熔融物。該擠出機的產出量是約6 kg/h。熔融物係經由水冷皮帶(參見第1圖的(d))移去,粉碎及研磨(參見第1圖的(e))。All solid components (phenolic resins used, Oxazoline, stabilizer, antioxidant, flame retardant) - in addition to epoxides and catalysts - mechanically premixed and fed into the extruder via a metering hopper (see Figure 1 (a)) 0. Simultaneously metered are the epoxides from two different storage containers (the storage container with a jacket temperature of 100 ° C, see (k) in Figure 1) and the catalyst solution (see Figure 1). (b)). The catalyst is fed to the melt in a solution having a concentration of 20% to 44% by weight. The extruder output is about 6 kg/h. The melt is removed via a water-cooled belt (see (d) of Fig. 1), pulverized and ground (see (e) of Fig. 1).
表3中顯示起始材料及其量。The starting materials and their amounts are shown in Table 3.
於規則時間間隔分析該擠出機排出物:The extruder effluent was analyzed at regular intervals:
‧ 藉由Tottoli(CH 320388)的方法測定所獲得的擠出機排出物之熔點。‧ The melting point of the obtained extruder effluent was determined by the method of Tottoli (CH 320388).
‧ 再者,製備該擠出機排出物於2-丁酮中的50重量%濃度溶液,並確定不溶物的重量分率。‧ Further, a 50% by weight concentration solution of the extruder effluent in 2-butanone was prepared, and the weight fraction of the insoluble matter was determined.
‧ 藉由示差掃描式熱分析儀(DSC)進行玻璃轉移溫度Tg 的測定。該擠出機排出物於10 K/min的加熱速率從25℃加熱至180℃,於180℃的鋁船中退火或固化6小時,按10 K/min的冷卻速率冷卻至25℃,及接著依據DIN 73765以10 K/min的加熱速率加熱至300℃來測定其玻璃轉移溫度Tg 。‧ The glass transition temperature T g was measured by a differential scanning thermal analyzer (DSC). The extruder effluent was heated from 25 ° C to 180 ° C at a heating rate of 10 K / min, annealed or cured in an aluminum vessel at 180 ° C for 6 hours, cooled to 25 ° C at a cooling rate of 10 K / min, and then The glass transition temperature T g was measured according to DIN 73765 by heating to 300 ° C at a heating rate of 10 K/min.
同樣使用這些分析技術測定比較例的產物性質。The analytical properties of the comparative examples were also determined using these analytical techniques.
表4中陳述實施例7至10的擠出機排出物之分析結果:The analysis results of the extruder discharges of Examples 7 to 10 are set forth in Table 4:
實施例9中看到的固體部分是難燃劑,其係呈固態存在及因此不溶於2-丁酮中;實施例10的案例中之性質類似。The solid portion seen in Example 9 was a flame retardant which was present in a solid state and thus was insoluble in 2-butanone; the properties in the case of Example 10 were similar.
這些發明例顯示在本發明方法的基礎之上,可藉由路易士加成物或三氟化硼製造預聚合物,其符合於酮中的安定性之要求。這些實施例顯示更特別的是此預聚合物具有低於120℃的熔點。可由該預聚合物製造的材料具有181至187℃的玻璃轉移溫度Tg 。These invention examples show that on the basis of the process of the invention, a prepolymer can be produced by a Lewis adduct or boron trifluoride, which meets the requirements for stability in ketones. These examples show that the prepolymer has a melting point below 120 °C. The material may be pre-fabricated polymer having a glass transition temperature of 181 to 187 deg.] C to T g.
所有固體(酚醛樹脂、唑啉、安定劑、抗氧化劑)以機械方式混合並經由計量料斗(參見第1圖的(a))輸入至該擠出機,同時計量觸媒(參見第1圖的(b))及由環氧化物和耐衝擊改質劑組成的混合物(具有50℃的夾套溫度之儲存容器,參見第1圖的(k))。該混合物係藉由於乾燥箱中將該耐衝擊改質劑加熱至60℃及使用螺漿攪拌器使其與環氧化物均質化而製造。該觸媒係呈40重量%濃度的溶液的形式輸入至該熔融物。該擠出機的產出量是約6 kg/h。熔融物係經由水冷皮帶移去,粉碎及研磨。All solids (phenolic resin, The oxazoline, stabilizer, antioxidant) are mechanically mixed and input to the extruder via a metering hopper (see (a) of Fig. 1) while measuring the catalyst (see (b) of Fig. 1) and A mixture of an epoxide and an impact modifier (a storage container having a jacket temperature of 50 ° C, see (k) of Figure 1). The mixture was produced by heating the impact modifier in a drying oven to 60 ° C and homogenizing it with an epoxide using a screw agitator. The catalyst was supplied to the melt in the form of a 40% by weight solution. The extruder output is about 6 kg/h. The melt is removed via a water-cooled belt, pulverized and ground.
該預聚合物的熔融範圍是68至86℃。The prepolymer has a melting range of 68 to 86 °C.
使25.39g的1,3-伸苯基雙唑啉、20.76g的酚醛樹脂(來自Sumitomo-Bakelite的Durez32311)、0.11g的抗氧化劑(來自Raschig的IONOL LC)及0.23g的安定劑(來自Cytec的Cyasorb3346)在玻璃燒杯中於140℃熔融大約30分鐘及攪拌大約5分鐘。等該熔融物已經冷卻至室溫之後藉由研缽將其均質化,在玻璃燒杯中於100℃熔融大約30分鐘及配合攪拌而與2.50g的環氧化物(來自Leuna Harze的EpiloxP13-20)及1.0g的潛在性觸媒(由等莫耳量的單水合對-甲苯磺酸(來自Merck)及二乙醇胺(來自Merck)製備,相當於0.64g=1.28%的單水合對-甲苯磺酸)摻混。讓起始材料再攪拌5分鐘及接著使該熔融物冷卻至室溫。固化之後玻璃轉移溫度Tg 是121℃,且固化係於180℃的溫度進行6小時。依據DIN 73765藉由示差掃描式熱分析儀(DSC)以10 K/min的加熱速率加熱至300℃來測定玻璃轉移溫度Tg 。Making 25.39g of 1,3-phenylene double Oxazoline, 20.76 g of phenolic resin (Durez from Sumitomo-Bakelite) 32311), 0.11g of antioxidant (IONOL LC from Raschig) And 0.23g of stabilizer (Cyasorb from Cytec) 3346) Melt in a glass beaker at 140 ° C for about 30 minutes and stir for about 5 minutes. After the melt has cooled to room temperature, it is homogenized by a mortar, melted in a glass beaker at 100 ° C for about 30 minutes and stirred with 2.50 g of epoxide (Epilox from Leuna Harze). P13-20) and 1.0 g of latent catalyst (prepared from monomolar monohydrate p-toluenesulfonic acid (from Merck) and diethanolamine (from Merck), equivalent to 0.64 g = 1.28% monohydrate pair -toluenesulfonic acid) blended. The starting material was stirred for a further 5 minutes and then the melt was allowed to cool to room temperature. The glass transition temperature T g after curing was 121 ° C, and the curing was carried out at a temperature of 180 ° C for 6 hours. The glass transition temperature T g was determined according to DIN 73765 by a differential scanning thermal analyzer (DSC) heated to 300 ° C at a heating rate of 10 K/min.
使用潛在性單水合對-甲苯磺酸/二乙醇胺(1.28%的單水合對-甲苯磺酸)得到具有玻璃轉移溫度Tg 為121℃之材料的預聚合物。A prepolymer having a glass transition temperature Tg of 121 ° C was obtained using the latent monohydrate p-toluenesulfonic acid / diethanolamine (1.28% mono-p-toluenesulfonic acid).
使25.68g的1,3-伸苯基雙唑啉、21.00g的酚醛樹脂(來自Sumitomo-Bakelite的Durez32311)、0.11g的抗氧化劑(來自Raschig的IONOL LC)及0.23g的安定劑(來自Cytec的Cyasorb3346)在玻璃燒杯中於140℃熔融大約30分鐘及攪拌大約5分鐘。等該熔融物已經冷卻至室溫之後藉由研缽將其均質化,在玻璃燒杯中於100℃熔融大約30分鐘及配合攪拌而與2.50g的環氧化物(來自Leuna Harze的EpiloxP13-20)及0.48g的潛在性觸媒(由等莫耳量的單水合對-甲苯磺酸(來自Merck)及二乙醇胺(來自Merck)製備,相當於0.31g=0.61%的單水合對-甲苯磺酸)摻混。讓起始材料再攪拌5分鐘及接著使該熔融物冷卻至室溫。固化之後玻璃轉移溫度Tg 是93.6℃,且固化係於180℃的溫度進行6小時。依據DIN 73765藉由示差掃描式熱分析儀(DSC)以10 K/min的加熱速率加熱至300℃來測定玻璃轉移溫度Tg 。Making 25.68g of 1,3-phenylene double Oxazoline, 21.00 g of phenolic resin (Durez from Sumitomo-Bakelite) 32311), 0.11g of antioxidant (IONOL LC from Raschig) And 0.23g of stabilizer (Cyasorb from Cytec) 3346) Melt in a glass beaker at 140 ° C for about 30 minutes and stir for about 5 minutes. After the melt has cooled to room temperature, it is homogenized by a mortar, melted in a glass beaker at 100 ° C for about 30 minutes and stirred with 2.50 g of epoxide (Epilox from Leuna Harze). P13-20) and 0.48 g of latent catalyst (prepared from monomolar monohydrate p-toluenesulfonic acid (from Merck) and diethanolamine (from Merck), equivalent to 0.31 g = 0.61% monohydrate pair -toluenesulfonic acid) blended. The starting material was stirred for a further 5 minutes and then the melt was allowed to cool to room temperature. The glass transition temperature T g after curing was 93.6 ° C, and the curing was carried out at a temperature of 180 ° C for 6 hours. The glass transition temperature T g was determined according to DIN 73765 by a differential scanning thermal analyzer (DSC) heated to 300 ° C at a heating rate of 10 K/min.
使用潛在性單水合對-甲苯磺酸/二乙醇胺(0.61%的單水合對-甲苯磺酸)得到具有玻璃轉移溫度Tg 為93.6℃之材料的預聚合物。A prepolymer having a glass transition temperature Tg of 93.6 °C was obtained using the latent monohydrate p-toluenesulfonic acid/diethanolamine (0.61% mono-p-toluenesulfonic acid).
使25.39g的1,3-伸苯基雙唑啉、20.76g的酚醛樹脂(來自Sumitomo-Bakelite的Durez32311)、0.11g的抗氧化劑(來自Raschig的IONOL LC)及0.23g的安定劑(來自Cytec的Cyasorb3346)在玻璃燒杯中於140℃熔融大約30分鐘及攪拌大約5分鐘。等該熔融物已經冷卻至室溫之後藉由研缽將其均質化,在玻璃燒杯中於100℃熔融大約30分鐘及配合攪拌而與2.50g的環氧化物(來自Leuna Harze的EpiloxP13-20)及1.4g的潛在性觸媒(由等莫耳量的單水合對-甲苯磺酸(來自Merck)及1-胺基-2-丙醇(來自Merck)製備,相當於1.0g=2%的單水合對-甲苯磺酸)摻混。讓起始材料再攪拌2分鐘,加入5.55g的Exolit AP 422(難燃劑)及接著使該熔融物冷卻至室溫。固化之後玻璃轉移溫度Tg 是113℃,且固化係於140℃的溫度進行3小時。在此之後接著於180℃後固化2小時,導致144℃的玻璃轉移溫度。依據DIN 73765藉由示差掃描式熱分析儀(DSC)以10 K/min的加熱速率加熱至300℃來測定玻璃轉移溫度Tg 。Making 25.39g of 1,3-phenylene double Oxazoline, 20.76 g of phenolic resin (Durez from Sumitomo-Bakelite) 32311), 0.11g of antioxidant (IONOL LC from Raschig) And 0.23g of stabilizer (Cyasorb from Cytec) 3346) Melt in a glass beaker at 140 ° C for about 30 minutes and stir for about 5 minutes. After the melt has cooled to room temperature, it is homogenized by a mortar, melted in a glass beaker at 100 ° C for about 30 minutes and stirred with 2.50 g of epoxide (Epilox from Leuna Harze). P13-20) and 1.4 g of latent catalyst (prepared from a molar amount of monohydrate p-toluenesulfonic acid (from Merck) and 1-amino-2-propanol (from Merck), equivalent to 1.0 g = 2% monohydrate p-toluenesulfonic acid) blended. The starting material was stirred for a further 2 minutes, 5.55 g of Exolit AP 422 (flammable agent) was added and the melt was then allowed to cool to room temperature. The glass transition temperature T g after curing was 113 ° C, and the curing was carried out at a temperature of 140 ° C for 3 hours. This was followed by post-curing at 180 °C for 2 hours, resulting in a glass transition temperature of 144 °C. The glass transition temperature T g was determined according to DIN 73765 by a differential scanning thermal analyzer (DSC) heated to 300 ° C at a heating rate of 10 K/min.
(a)...固態組分(a). . . Solid component
(b)...觸媒(b). . . catalyst
(c)...產物排出位置(c). . . Product discharge location
(d)...水冷皮帶(d). . . Water cooled belt
(e)...研磨(e). . . Grinding
(f)...細粒(f). . . Fine grain
(g)...套筒(g). . . Sleeve
(h)...螺桿傳動(h). . . Screw drive
(i)...擠出機頭部(i). . . Extruder head
(k)...環氧化物(k). . . Epoxide
0...筒0. . . cylinder
1...筒1. . . cylinder
2...筒2. . . cylinder
3...筒3. . . cylinder
4...筒4. . . cylinder
5...筒5. . . cylinder
6...筒6. . . cylinder
7...筒7. . . cylinder
第1圖是根據本發明的多筒式擠出機之示意圖。Figure 1 is a schematic illustration of a multi-cylinder extruder in accordance with the present invention.
(a)...固態組分(a). . . Solid component
(b)...觸媒(b). . . catalyst
(c)...產物排出位置(c). . . Product discharge location
(d)...水冷皮帶(d). . . Water cooled belt
(e)...研磨(e). . . Grinding
(f)...細粒(f). . . Fine grain
(g)...套筒(g). . . Sleeve
(h)...螺桿傳動(h). . . Screw drive
(i)...擠出機頭部(i). . . Extruder head
(k)...環氧化物(k). . . Epoxide
0...筒0. . . cylinder
1...筒1. . . cylinder
2...筒2. . . cylinder
3...筒3. . . cylinder
4...筒4. . . cylinder
5...筒5. . . cylinder
6...筒6. . . cylinder
7...筒7. . . cylinder
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2011
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- 2011-11-14 TW TW100141453A patent/TWI513723B/en not_active IP Right Cessation
- 2011-11-15 CA CA2758420A patent/CA2758420C/en not_active Expired - Fee Related
- 2011-11-16 US US13/297,906 patent/US8834971B2/en not_active Expired - Fee Related
- 2011-11-16 CN CN2011103630150A patent/CN102532489A/en active Pending
- 2011-11-16 KR KR1020110119589A patent/KR101896118B1/en active IP Right Grant
- 2011-11-17 JP JP2011251729A patent/JP5954963B2/en not_active Expired - Fee Related
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Also Published As
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EP2455424A1 (en) | 2012-05-23 |
CN102532489A (en) | 2012-07-04 |
EP2455424B1 (en) | 2014-01-01 |
US8834971B2 (en) | 2014-09-16 |
DE102010044050A1 (en) | 2012-05-24 |
KR20120053472A (en) | 2012-05-25 |
JP2012107240A (en) | 2012-06-07 |
BRPI1105582A2 (en) | 2014-03-18 |
BRPI1105582B1 (en) | 2020-09-15 |
KR101896118B1 (en) | 2018-09-07 |
CA2758420A1 (en) | 2012-05-17 |
CA2758420C (en) | 2018-10-16 |
US20120121812A1 (en) | 2012-05-17 |
JP5954963B2 (en) | 2016-07-20 |
TW201235373A (en) | 2012-09-01 |
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